Carbon Black Samples Research Articles

Determination of heavy metals in activated charcoals and carbon black for Lyocell fiber production using direct solid sampling high-resolution continuum source graphite furnace atomic absorption and inductively coupled plasma optical emission spectrometry

Reactivity and concentration of additives, especially activated charcoal, employed for the Lyocell process, enhance the complexity of reactions in cellulose/N-methylmorpholine-N-oxide monohydrate solutions. Analytical control of the starting materials is a basic requirement to know the concentration of heavy metals, which are potential initiators of autocatalytic reactions. Seven activated charcoal and two carbon black samples have been analyzed regarding their content of seven elements, Cr, Cu, Fe, Mn, Mo, Ni and V using direct solid sampling high-resolution continuum source graphite furnace AAS (SS-HR-CS GF AAS) and inductively coupled plasma optical emission spectrometry (ICP OES) after microwave-assisted acidic digestion as a reference method. The limits of detection of the former technique are 1-2 orders of magnitude lower than those of ICP OES and comparable to those of more sophisticated techniques. For iron the working range of HR-CS GF AAS has been expanded by simultaneous measurement at two secondary absorption lines (344,099nm and 344,399nm). Partial least-squares regression between measured and calculated temperatures for beginning exothermicity (T(on)) has been used to investigate the prediction capability of the investigated techniques. Whereas the ICP OES measurements for seven elements resulted in an error of prediction of 3.67%, the results obtained by SS-HR-CS GF AAS exhibited a correlation coefficient of 0.99 and an error of prediction of only 0.68%. Acceptable correlation has been obtained with the latter technique measuring only three to four elements.

Specific anion and cation capacitance in porous carbon blacks

Porous carbon black was modified to introduce oxygen and nitrogen surface functionality and characterized using wet titration methods, elemental analysis, XPS, TEM, thermal analysis, adsorption of nitrogen and carbon dioxide. Then the electrochemical capacitance was measured for cations and anions in 1 M H 2SO 4. The results were compared to those obtained on activated carbons. The modified carbon black samples have four times higher adsorption of anions than cations. It is hypothesized that the graphitic microstructure of carbon blacks with structural defects is responsible for intercalation of anions in-between the graphene layers which take place at potentials higher than 0.75 V vs. Ag/AgCl and at moderately low current loads. This process is reversible and the deintercalation occurs at approximately 0.4 V vs. Ag/AgCl during the cathodic reduction. Introduction of nitrogen have generally a detrimental effect on the anion adsorption capacitance due to a structural defects blockage. At high current loads this phenomenon of enhanced anion adsorption capacitance becomes less pronounced due to the kinetic limitations. For amorphous activated carbons enhanced anion electrosorption at low current loads is governed by proton assistance while at high current loads larger cation capacitance is due to the pseudocapacitive interactions of protons with nitrogen and oxygen functional groups.

Quantification of Extraneous Carbon during Compound Specific Radiocarbon Analysis of Black Carbon

Radiocarbon ((14)C) is a radioactive isotope that is useful for determining the age and cycling of carbon-based materials in the Earth system. Compound specific radiocarbon analysis (CSRA) provides powerful insight into the turnover of individual components that make up the carbon cycle. Extraneous or nonspecific background carbon (C(ex)) is added during sample processing and subsequent isolation of CSRA samples. Here, we evaluate the quantity and radiocarbon signature of C(ex) added from two sources: preparative capillary gas chromatography (PCGC, C(PCGC)) and chemical preparation of CSRA of black carbon samples (C(chemistry)). We evaluated the blank directly using process blanks and indirectly by quantifying the difference in the isotopic composition between processed and unprocessed samples for a range of sample sizes. The direct and indirect assessment of C(chemistry+PCGC) agree, both in magnitude and radiocarbon value (1.1 +/- 0.5 microg of C, fraction modern = 0.2). Half of the C(ex) is introduced before PCGC isolation, likely from coeluting compounds in solvents used in the extraction method. The magnitude of propagated uncertainties of CSRA samples are a function of sample size and collection duration. Small samples collected for a brief amount of time have a smaller propagated (14)C uncertainty than larger samples collected for a longer period of time. CSRA users are cautioned to consider the magnitude of uncertainty they require for their system of interest, to frequently evaluate the magnitude of C(ex) added during sampling processing, and to avoid isolating samples < or = 5 microg of carbon.

Characterisation of black carbon materials by pyrolysis–gas chromatography–mass spectrometry

Pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS) was used to investigate the chemical structures of eight black carbon (BC) materials: hexane soot, gasoline soot, diesel soot, coal soot, grass soot, wood soot, grass charcoal and wood charcoal. Py–GC–MS data revealed that the pyrolytic products of the eight BC samples were all dominated in aromatic compounds, followed by smaller amounts of aliphatic compounds. O-containing pyrolytic products were also present in all eight BC samples. The data suggest that the structures of eight BCs were composed of highly aromatic structures that were cross-linked by aliphatic chain-like bridges and/or O-containing polar functional groups. Owing to the different fuel precursors and combustion conditions, the eight BC materials also differed in many respects. The pyrolytic products from soot BCs contained higher amounts of N-containing compounds, reflecting the combustion conditions. S-containing compounds were only present in pyrolytic products from three fossil-fuel soots, and can be used as a marker for soot from fossil fuels. Charcoal BCs can retain some plant structure, containing significant amounts of typical lignin-derived phenolic compounds. The results may be useful for interpretation of Py–GC–MS data for complicated BCs isolated from soils, sediments and aerosols.

Methane catalytic decomposition over ordered mesoporous carbons: A promising route for hydrogen production

Methane decomposition offers an interesting route for the CO 2-free hydrogen production. The use of carbon catalysts, in addition to lowering the reaction temperature, presents a number of advantages, such as low cost, possibility of operating under autocatalytic conditions and feasibility of using the produced carbons in non-energy applications. In this work, a novel class of carbonaceous materials, having an ordered mesoporous structure (CMK-3 and CMK-5), has been checked as catalysts for methane decomposition, the results obtained being compared to those corresponding to a carbon black sample (CB-bp) and two activated carbons, presenting micro- (AC-mic) and mesoporosity (AC-mes), respectively. Ordered mesoporous carbons, and especially CMK-5, possess a remarkable activity and stability for the hydrogen production through that reaction. Under both temperature programmed and isothermal experiments, CMK-5 has shown to be a superior catalyst for methane decomposition than the AC-mic and CB-bp materials. Likewise, the catalytic activity of CMK-5 is superior to that of AC-mes in spite of the presence of mesoporosity and a high surface area in the latter. The remarkable stability of the CMK-5 catalyst is demonstrated by the high amount of carbon deposits that can be formed on this sample. This result has been assigned to the growth of the carbon deposits from methane decomposition towards the outer part of the catalyst particles, avoiding the blockage of the uniform mesopores present in CMK-5. Thus, up to 25 g of carbon deposits have been formed per gram of CMK-5, while the latter still retains a significant catalytic activity.

Reduction of Cr(VI) by Crop-Residue-Derived Black Carbon

Burning crop residues is a common postharvest practice on farmland, leading to the accumulation of black carbon (BC) in the soil. To understand the potential role of BC in immobilizing toxic Cr(VI) in soil, this study evaluated the Cr(VI) sorption kinetics at pH levels ranging from 3 to 7 and examined the reaction mechanism of Cr(VI) with BC derived from burning rice straw. The BC samples, after reacting with Cr(VI), were analyzed using Cr K-edge X-ray absorption spectroscopy. The results showed that Cr(VI) was sorbed and subsequently reduced to Cr(III), which was bound to the BC surface through surface complexation and precipitation. As indicated by the diffuse reflection infrared Fourier transform spectra, the phenolic groups of BC are the dominant drivers of Cr(VI) reduction, giving rise to carbonyl/carboxyl groups on the BC surface. The reaction rate of Cr(VI) with BC increased from 10(-3.62) to 10(-1.65) h(-1) as pH was decreased from 7 to 3 because Cr(VI) sorption and reduction both occur faster at low pH. These results suggest that BC derived from burning crop residue is an effective reductant for Cr(VI) and may play an important role in determining the fate of Cr(VI) in BC-rich farmland soils.

Determination of elemental carbon in lake sediments using a thermal–optical transmittance (TOT) method

An improved chemical oxidation pretreatment method has been developed for the determination of elemental carbon (EC) [also known as black carbon (BC) or soot] in lake sediments, using a thermal–optical transmittance (TOT) carbon analyzer. The method employs six steps: (1) removal of carbonates by treatment with HCl; (2) removal of silicates by treatment with HF + HCl; (3) removal of any remaining carbonates by treatment with HCl; (4) removal of humic acids by treatment with NaOH; and (5) oxidation of kerogens by K 2Cr 2O 7 + H 2SO 4. A critical step of zinc chloride treatment was added; this apparently changes EC's morphology and enhances retention on quartz fiber filter, resulting in several-fold increased chemical yield. EC was determined using the TOT method with modified combustion timings. Carbon black (acetylene) and four NIST standard reference materials (SRMs) were used for quality control, and to assess the precision of the analysis. The EC recoveries from 18 carbon black samples varied from 90 to 111%, with a mean value of 99 ± 6%. The high EC recoveries confirmed the validity of the method. Char reference materials (i.e. chestnut wood and grass char) were used to determine potential contribution to EC in our measurements. The char references containing about 700 mg total organic carbon (OC) contributed ∼1.5% EC. The measured EC values from four NIST standards were 17.0 ± 0.6, 24.2 ± 3.2, 5.6, and 1.9 ± 0.1 mg g dw −1 for SRM-1648, SRM-1649a, SRM-1941b and SRM-8704, respectively. These values in SRMs were in agreement (<±4%) with the previously reported values. The method was applied to determine the EC in sediment cores from an urban lake and a remote mountain lake in the Northeastern United States. The EC concentrations in two lakes mimic the model EC emissions from the industrial revolution in United States.

Dispersion medium modulates oxidative stress response of human lung epithelial cells upon exposure to carbon nanomaterial samples

Due to their large specific surface area, the potential of nanoparticles to be highly reactive and to induce oxidative stress is particularly high. In addition, some types of nanoparticles contain transition metals as trace impurities which are known to generate reactive oxygen species (ROS) in biological systems. This study investigates the potential of two types of single-walled carbon nanotube samples, nanoparticulate carbon black and crocidolite asbestos to induce ROS in lung epithelial cells in vitro. Carbon nanotube and carbon black samples were used as produced, without further purification or processing, in order to best mimic occupational exposure by inhalation of airborne dust particles derived from carbon nanomaterial production. Intracellular ROS were measured following short-term exposure of primary bronchial epithelial cells (NHBE) and A549 alveolar epithelial carcinoma cells using the redox sensitive probe carboxydichlorofluorescin (carboxy-DCFDA). The oxidative potential of agglomerated nanomaterial samples was compared following dispersion in cell culture medium with and without foetal calf serum (FCS) supplement. In addition, samples were dispersed in dipalmitoylphosphatidylcholine (DPPC), the major component of lung surfactant. It could be illustrated that in vitro exposure of lung epithelial cells to carbon nanomaterial samples results only in moderate or low oxidative stress under the exposure conditions employed. However, cell responses are strongly dependent on the vehicle used for dispersion. Whereas the presence of DPPC increased intracellular ROS formation, FCS seemed to protect the cells from oxidative insult.

Composition and textural properties of soot and study of their oxidative elimination by catalytic process

Diesel soot and reference carbon black samples have been characterised by analysis of the organic compounds fraction and determination of textural characteristics (specific area). The potential to eliminate such carbonaceous particles has been investigated using a Cu/ZrO2 solid catalyst promoted by potassium additives. The reactivity of soot samples depends on the organic compounds content. In general, Cu-K/ZrO2 catalyst is able to lower significantly the soot oxidation temperature of almost 200°. This high activity is related to the ability of potassium to interact with copper species and to favour the release of active oxygen from the catalyst.

Study of the deactivation mechanism of carbon blacks used in methane decomposition

Carbon blacks have recently gained attention as suitable catalysts for the CO x -free hydrogen production by thermo-catalytic decomposition of methane (TCD) because of their stability and efficiency. In the present work, several commercial carbon blacks were studied as catalysts for the TCD of methane by varying the temperature and the methane space velocity. The BP2000 carbon black sample, which showed the highest activity in methane decomposition per mass of catalyst, was studied more thoroughly. Despite BP2000 exhibiting stable activity in the TCD of methane during several hours on stream, a long duration run carried out at 950 °C revealed that it finally became deactivated. The changes in the physicochemical properties (textural properties, surface chemistry and crystallinity) of the BP2000 sample at different stages of the catalyst lifetime were measured, and the main results obtained are presented here. The paper also discusses the potential of the production of a wide range of hydrogen–methane mixtures, which can be directly fed to an internal combustion engine, by means of TCD with carbonaceous catalysts.

Stability of black carbon in soils across a climatic gradient

The recalcitrant properties of black carbon (BC) grant it to be a significant pool of stable organic C (OC) in soils. Up to now, however, the longevity of BC under different climates is still unclear. In this study, we used BC samples from historical charcoal blast furnace sites to examine the stability of BC across a climatic gradient of mean annual temperatures (MAT) from 3.9 to 17.2°C. The results showed that OC concentration and OC storage in the BC‐containing soils at a soil depth of 0–0.2 m were 9.0 and 4.7 times higher than those in adjacent soils, respectively. Organic C in the BC‐containing soils was more stable, with a significantly lower amount of the labile OC fraction (4.4 mg g−1 OC versus 27.5 mg g−1 OC) and longer half‐life of the recalcitrant OC fraction (59 years versus 9 years) than the adjacent soils determined by incubation experiments. The stability of BC was primarily due to its inherently recalcitrant chemical composition as suggested by short‐term incubation and solid state 13C nuclear magnetic resonance spectra of isolated BC particles. A significant negative relationship between OC storage and MAT further indicated that OC storage was decreased with warmer climate. However, the lack of a relationship between MAT and BC mineralization suggested that the stability of the remaining BC was similar between sites with very different MAT. Despite the fact that warming or cooling result in immediate consequences for BC stocks, it may have little impact on the stability of remaining BC over the period studied.

Fourier Transform Infrared Measurement of Solid-, Liquid-, and Gas-Phase Samples with a Single Photoacoustic Cell

A photoacoustic detector based on the optical cantilever microphone has been built. The detector is capable of measuring solid-, liquid-, and gas-phase samples. Photoacoustic Fourier transform infrared (FT-IR) measurement with three samples in different phases was demonstrated. Example samples were polyethene, sunflower oil, and methane. The sensitivity of the cell was compared to a commercial photoacoustic FT-IR detector. With the standard carbon black sample the cantilever detector gave approximately five times higher signal-to-noise ratio than the reference detector. The sensitivity with methane was also compared to the DTGS detector of the FT-IR instrument corresponding to an absorption path of 6.3 cm. Simulation of the photoacoustic signal showed that a compromise has to be made in the cell design between sensitivity for solid- and gas-phase samples but it is possible to highly enhance the sensitivity for all types of samples by reducing cantilever dimensions.

Natural oxidation of black carbon in soils: Changes in molecular form and surface charge along a climosequence

The aim of this work was to investigate changes in molecular form and surface charge of black carbon (BC) due to long-term natural oxidation and to examine how climatic and soil factors affect BC oxidation. Black C was collected from 11 historical charcoal blast furnace sites with a geographic distribution from Quebec, Canada, to Georgia, USA, and compared to BC that was newly produced (new BC) using rebuilt historical kilns. The results showed that the historical BC samples were substantially oxidized after 130 years in soils as compared to new BC or BC incubated for one year. The major alterations by natural oxidation of BC included: (1) changes in elemental composition with increases in oxygen (O) from 7.2% in new BC to 24.8% in historical BC and decreases in C from 90.8% to 70.5%; (2) formation of oxygen-containing functional groups, particularly carboxylic and phenolic functional groups, and (3) disappearance of surface positive charge and evolution of surface negative charge after 12 months of incubation. Although time of exposure significantly increased natural oxidation of BC, a significant positive relationship between mean annual temperature (MAT) and BC oxidation (O/C ratio with r = 0.83; P < 0.01) explained that BC oxidation was increased by 87 mmole kg C −1 per unit Celsius increase in MAT. This long-term oxidation was more pronounced on BC surfaces than for entire particles, and responded 7-fold stronger to increases in MAT. Our results also indicated that oxidation of BC was more important than adsorption of non-BC. Thus, natural oxidation of BC may play an important role in the effects of BC on soil biogeochemistry.

The Study of Adsorption of Iodine on Carbon Black by Inverse Liquid Chromatography

Abstract The study of iodine adsorption on carbon black samples was made using inverse liquid chromatographic frontal analysis (ILC). Unlike HPLC supports, the efficiency of the chromatographic column filled with a carbon black designed for rubber applications is low. Then the front boundaries of a non-adsorbed molecule, like heavy water (D2O) or acetone, was taken as reference for the calculation of the desorption isotherms. The monolayer capacity of adsorption, Langmuir's and Henry's constants were determined from the desorption isotherms. It was observed that 40% of the surface of the studied carbon black corresponds to a phenomenon of irreversible adsorption of the probe, and that the ILC also highlighted the heterogeneity of the studied carbon black. The adsorption energy distribution functions of iodine obtained by this method are similar to those which were already determined by IGC-FC with the heptane -like probe. The differences in behaviors between two families of carbon black could be attributed to the surface roughness.

Particle size and zeta potential of carbon black in liquid media

Zeta potential is a parameter that can be used for studying and predicting colloid stability and surface morphology. Even though zeta potential measurements have been applied to both aqueous and non-aqueous suspensions, theories for colloidal behavior and zeta potential in non-aqueous media are not as well-established as those in aqueous environments. There are few reports on systematic studies of zeta potential of colloids in liquid media. In the present study, zeta potential and particle size measurements of two carbon black powder samples in various media were performed. Combined with particle size characterization, the experimental zeta potential values were used to discuss charge transfer and colloid stability of carbon black in suspension.

Surface characteristics of crop-residue-derived black carbon and lead(II) adsorption

Previous studies demonstrated that black carbon (BC) in soils arising from the burning of crop residues is a highly effective adsorbent for organic contaminants. This work evaluated the adsorptive ability of BC for heavy metals in relation to the BC surface characteristics. Two BC samples, rice carbon (RC) and wheat carbon (WC) isolated from the burning residues of rice straw and wheat straw, respectively, were characterized for their surface properties with reference to a commercial activated carbon (AC). While RC and WC had lower surface areas than AC, the two BC samples possessed higher surface acidities and thus lower pH of the isoelectric points (pH IEP) than AC as indicated by titration, FTIR, and zeta potential measurements. The Pb(II) adsorption by RC and WC was higher than that by AC and increased significantly with increasing pH, suggesting the electrostatic interactions between positive Pb(II) species and negatively charged functional groups on RC and WC as the primary adsorptive forces. A reduction in the total positive charge of Pb(II) species with increasing pH as computed by MINTEQA2 suggested that the deprotonation of surface functional groups of RC and WC was the controlling factor of the adsorption. The Pb(II) adsorption decreased with increasing ionic strength, due to the screening role of Na + in neutralizing the negative charge of RC and WC. This study demonstrated that BC may be an important adsorbent of heavy metals in soil and that the adsorption may be significantly influenced by environmental conditions.

Hydrogen production by methane decarbonization: Carbonaceous catalysts

Decarbonization of natural gas by thermo-catalytic decomposition, TCD, to produce hydrogen and carbon is a very attractive alternative to steam methane reforming (SMR) for small-to-medium size facilities because by TCD, the carbon contained in natural gas is collected as a solid, marketable product. In this paper, the use of different carbon blacks with a high external surface area, easily accessible to methane molecules has been explored as an alternative to activated carbons. Carbon blacks with high surface area provide relatively high methane decomposition rate. While for the activated carbon there was a rapid deactivation, for the carbon black samples, the process goes on until most of the surface is covered by carbon crystallites produced from methane. The surface chemistry and the pore size distribution play an important role on the initial rate conversion of methane and the long term sustainability of the catalyst, respectively.

Evaluation of the thermal/optical reflectance method for discrimination between char- and soot-EC

Many optical, thermal and chemical methods exist for the measurement of elemental carbon (EC) but are unable or neglect to differentiate between the different forms of EC such as char- or soot-EC. The thermal/optical reflectance (TOR) method applies different temperatures for measuring EC and organic carbon (OC) contents through programmed, progressive heating in a controlled atmosphere, making available eight separate carbon fractions – four OC, one pyrolyzed organic carbon, and three EC. These fractions were defined by temperature protocol, oxidation atmosphere, and laser-light reflectance/transmittance. Stepwise thermal evolutional oxidation of the TOR method makes it possible to distinguish char- from soot-EC. In this study, different EC reference materials, including char and soot, were used for testing it. The thermograms of EC reference materials showed that activation energy is lower for char- than soot-EC. Low-temperature EC1 (550 °C in a 98% He/2% O 2 atmosphere) is more abundant for char samples. Diesel and n-hexane soot samples exhibit similar EC2 (700 °C in a 98% He/2% O 2 atmosphere) peaks, while carbon black samples peaks at both EC2 and EC3 (800 °C in a 98% He/2% O 2 atmosphere). These results supported the use of the TOR method to discriminate between char- and soot-EC.

HRTEM Study of diesel soot collected from diesel particulate filters

HRTEM study of several soot samples collected on Diesel Particulate Filters (DPF) under conditions relevant to practical applications of DPF technology, revealed nano-structure, to our knowledge, not reported previously for diesel soot. In particular, some of the primary particles were found to have hollow interior, and the outer shell exhibiting evidence of graphitization, with a higher crystallinity compared to the non-hollowed particles. The percentage of such particles varied between different soot samples and tentatively appeared to be related to the oxidation history of the sample. Remarkably, similar effect was not reproduced for a carbon black sample, Printex-U, suggesting that propensity to such oxidation-induced graphitization is related to the original nano-structure of the particle. These initial observations were independently confirmed for the same set of soot samples by two different HRTEM facilities, at NASA-Glenn and PNNL.

Steam activation of tyre pyrolytic carbon black: Kinetic study in a thermobalance

Kinetic parameters for the steam activation of tyre pyrolytic carbon black have been determined by thermogravimetric analysis (TGA). Pyrolytic carbon black is a mainly macro and mesoporous material whose surface area can be improved via gasification to obtain microporous activated carbons. The pyrolytic carbon black sample was produced in an experimental-scale assembly where shredded tyre was pyrolysed under controlled conditions in a fixed bed reactor. Then, the activation of the resulting solid was studied by TGA using steam as activating agent. Kinetic regime was ensured fixing experimental conditions and therefore, avoiding internal and external mass transfer and heat transmission phenomena. Temperature (850–950 °C) and activating gas concentration (10–40 vol.%) were the influencing variables under study. This is the first time that the random pore model (RPM) has been used to fit experimental data of the activation of pyrolytic carbon black with steam. Excellent fittings have been obtained because of the special applicability of this model to predict the behaviour of solid–fluid reactive systems, in which the solid phase shows a porous structure. Reaction evolution has successfully been modelled, including the maximum reaction rate obtained in experimental results. Additionally, intrinsic kinetic parameters of the activation reaction–reaction order, activation energy and pre-exponential factor – were calculated.